Fluorination of saturated halocarbons with cerium tetrafluoride



Patented Jan. 3, 1950 ATIEN ori FLUORINATION OF SATURATED HALOCAR- BONS WITH CERIUM TETRAFLUORIDE Earl T. McBee, La Fayette, Ind, Richard M. Robb, Wilmington, Del., and Waldo B. Ligett, Detroit, Mich., assignors to Purdue Research Founda-- tion, La Fayette, 1nd,, a corporation of Indiana No Drawing. Application March 14, 1946,

Serial No. c54.522

This invention relates to organic compounds containing fluorine, particularly to saturated fluorine-containing halocarbons, and to a method for the preparation thereof. This application is a continuation in part of application Serial No. 596,967, filed May 31, 1945.

The preparation of fluorine-containing halocarbons, i. e., of fluorine-containing compounds composed entirely of carbon and halogen, has, in most instances, heretofore been attended with considerable difllculty. It is well known that elemental fluorine generally may not be reacted with organic compounds, even with halohydrocarbons containing a low proportion of hydrogen, and the reaction controlled so as to produce a desired fluorine-containing halocarbon. Although certain halogens other than fluorine, e. g., chlorine and bromine, may react with a wide variety of organic compounds under suitable conditions to give high yields of valuable products, the reac-' tion of fluorine with most organic compounds is violent in nature and is usually accompanied by profound decomposition of the organic compound. In most cases, reaction occurs with explosive violence in spite of extreme measures which may be taken to moderate its effect. In many instances, the reaction products consist mainly ofcarbonaceous matter and hydrogen fluoride or of other equally undesirable products. Whem using a large excess of fluorine,the principal products are generally carbon tetrafluoride and hydrogen fluoride.

Many attempts have been made to use fluorinating agents other than elemental fluorine to replace halogen or hydrogen in organic compounds to obtain desired fluorine-containing compounds, e. g., fluorine-containing halocarbons. Among the fiuorinating agents which have been tried may be mentioned hydrogen fluoride, antimony trifluoride, mercuric fluoride, iodine pentafluoride, bromine trifluoride, chlorine trifluoride, and many others. Although certain of these agents may, under certain conditions, replace with fluorine a certain proportion of an existing halogen 'atom other than fluorine already in a halocarbon molecule, many of these agents are expensive to prepare and inconvenient to work with. Furthermore, highly fluorinated compounds, e. g., perfluorinated compounds, are not usually obtained readily from the corresponding highly chlorinated, brominated or iodinated compounds using such agents. Certain of the agents referred to, e. g., the bromine trifluoride, react with many organic compounds with explosive violence.

6' Claims. (Ci. 260%48) rinated products.

2 Most metal fluorides heretofore proposed as agents to replace chlorine, bromine or iodine in organic compounds with fluorine tend, under the conditions necessary to obtain a high degree of exchange of halogen, to produce polymerized or unsaturated break-down products and frequently do not lead to complete or uniform replacement of chlorine, bromine or iodine with fluorine. For these and other reasons, fluorine-containing halocarbons have not heretofore been available except in a few instanceaand industry has been deprived of many members of this valuable group of compounds. The need for new and improved procedures for the preparation of fluorine-containing halocarbons is evident.

It is, therefore, an object of the present invention to provide a method for the preparation of fluorine-containing halocarbons. Still a further object is to provide a method whereby saturated fluorine-containing halocarbons, includingfluorocarbons, may be prepared from completely chlorinated, brominated or iodinated saturated hydrocarbons. An additional object is to provide a method whereby fluorine-containing halocarbons may be prepared from completely halogenated hydrocarbons containing two or more different halogens. An additional object is to provide a method for increasing the fluorine content of a halocarbon containing fluorine and another halogen. An additional object is to provide a method for preparing a fluorine-containing halocarbon whereby the formation of undesirable decomposition or polymerization products is substantially avoided.- An additional object is to provide a method for fluorinating a halocarbon containing a halogen other than fluorine whereby a predetermined degree of fluorination may be effected readily. An additional object is to provide a fluorination method which is not subject to certain of the disadvantages set forth above. Still a further object is to provide a novel fluorinating agent capable of replacing established halogen other than fluorine in halocarbons with fluorine. Still an additional object is to provide certain new and novel fluorine-containing halocarbons,

including fluorocarbons and other highly fluo- Other objects will become apparent from the following specification and claims.

, According to the present invention, the foregoing and related objects are accomplished readily and economically by contacting a saturated halocarbon containing in the molecule at least one atom of halogen other than fluorine with cerium tetrafluoride under suitable reaction conditions until a desired degree of replacement with fluorineof said halogen other than fluorine has occurred, and separating from the reaction mixture a halocarbon containing at least a higher .proportion of fluorine than the halocarbon tion products. Saturated aliphatic and alicyclic halocarbons, including fused-ring halocarbons and polycarbocyclic non-fused-ring halocarbons, can be converted readily to fluorinecontaining halocarbons. Chlorine, bromine and iodine present in the halocarbon reactant can be replaced partially or completely with fluorine, as desired. Examples of saturated fluorine-containing halocarbons containing at least one halogen atom other than fluorine which may be prepared by the method of the invention include monochlorotrifluoromethane, dichlorodifluoromethane, trichloromonofluoromethane, tetrachlorodifluoroethane, dichlorotetrafluoroethane, monobromomonochlorotetrafluoroethane, monobromopentafluoroethane, dichlorodecafluorocyclohexane, dichloro- -tetradecafiuoroheptane, pentafluoromonoiodoethane, undecachloroundecafluorobicyclohexyl, dichlorohexadecafluoronaphthalane, and many others. Saturated fluorine-containing halocarbons containing at least one halogen atom other than fluorine in the molecule, such as those just mentioned may be fluorinated to form saturated halocarbons of increased fluorine content including fluorocarbons, if desired.

- other than fluorine in the molecule with cerium tetrafluoride as an active fluorinating agent under such conditions and for such time that all of such halogen other than fluorine in the molecule is replaced by fluorine; Examples of fluorocarbons which may be prepared by such perfluorination procedure include carbon tetrafluoride, hexafluoroethane, dodecafluoropentane, dodecafluorocyclohexane, tetradecafluoromethylcyclohexane, perfluorobicyclohexyl, perfluoronaphthalane and many others.

In certain instances, rupture of the molecule may be effected with the formation of saturated fluorine-containing halocarbons having 'fewer carbon atoms in the molecule than does the original halocarbon fluorinated. -This is herein referred to as fluorinolysis. Thus high molecular weight saturated halocarbons may, for example, be converted largely to high molecular weight fluorine-containing halocarbons, to high molecular weight saturated fluorocarbons. or, under more vigorous reaction conditions to saturated fluorine-containing halocarbons or fluorocarbons having fewer carbon atoms in the molecule, such as hexafluoroethane and even carbon tetrafluoride, if desired.

The fluorination reaction is exothermic; however, it proceeds without explosive violence and carried out in cyclical manner, the cerium tetrafluoride being first contacted with a saturated halocarbon reactant to produce a desired saturated fluorine-containing halocarbon and the spent cerium tetrafluoride. consisting largely of cerium trifluoride, then regenerated with elemental fiuorine and the cycle repeated. Furthermore, it may be desirable in some instances when a highly fluorinated saturated halocarbon is desired, to effect only partial fluorination in the first passage of the halocarbon reactant through the fluorination reactor and then to recycle the fluorine-containing product over regenerated or fresh cerium tetrafluoride to increase the proportion of fluorine in the halocarbon molecule. Recycling of the fluorine-containing halocarbon as well as of the cerium fluoride may be continued until a fluorocarbon is obtained, if desired.

Cerium tetrafluoride is a solid which is unstable in the presence of water or atmospheric moisture.

The compound is substantially stable, when dry at temperatures as high as 500' C. and higher. Cerium tetrafluoride may be preparedreadily in a number of ways, one convenient way being by the treatment of anhydrous cerium trifluoride with elemental fluorine at an elevated temperature, e. -g., at a temperature above about 200 0., preferably at a temperature between about 400 C. and about 500 C. Cerium trifluoride may be prepared readily by treating anhydrous cerium trichloride with anhydrous hydrogen fluoride at temperatures above about 200 C., by precipitation from a solution of a soluble cerium salt e. g., cerous nitrate with hydrogen fluoride or a soluble metal fluoride, filtering and drying, and in many other ways. I

In practicing the invention, it has been found convenient to place anhydrous cerium trifluoride in the reaction vessel in which the subsequent fluorination of a saturated halocarbon is to be Fluorination of a saturated halocarbon with cerium tetrafluoride may be carried out in any convenient manner and many convenient type of apparatus. It has been found satisfactory to dispose the cerium tetrafluoride in a thin layer, e. g., in a layer from about one-half to about one inch thick, on shelves or trays within the reaction vessel or directly on the floor of the vessel itself and to pass the halocarbon in vapor form through 4 th vessel. The process is frequently carried out I by distributing a shallow layer of cerium tetrafluoride throughout the length of a metal tube and passing a saturated halocarbon in vapor form through the tube. If desired, tubes with rectangular cross section may be used and the exposed surface of the layer of cerium tetrafluoride thus increased. The mass may be agitated, it desired. The physical form of the cerium tetrafluoride is preferably such that easy penetration of the mass of tetraiiuoride by gases or vapors passing through the reaction vessel is facilitated. Granulated or coarsely powdered cerium tetrafluorlde has been found to be satisfactory.

The reaction vessel, which may be of iron, nickel or other material resistant to the reactants and reaction products under the conditions of fluorinatlon and regeneration, is maintained at a desired reaction temperature by any convenient means. Heating may be efi'ected in any one of a number of ways, such as by electrical resistance heaters, by gas flames, or by immersing the reaction vessel in a suitable high-boiling liquid, such as a low-melting alloy. The fluorinatlon reaction is exothermic in nature and in large size reaction vessels heatingmay not be necessary after the reaction has started. In some instances, cooling may even be advisable.

Fluorination of a. saturated halocarbon with cerium tetrafluoride may be carried out with the halocarbon reactant in either liquid or gaseous phase. In practice, however, it has usually been found more convenient, especially when high temperatures are required, to pass'the halocarbon reactant through the reactor in vaporform. In this way the handling of organic liquids at high temperatures is avoided and the reaction may be carried out at ordinary pressures. A saturated halocarbon reactant may be introduced into the reaction vessel either in the form of its vapor or as a liquid. In the latter instance, the halocarbon is usually vaporized in the portion of the reaction vessel nearest the entry port and the vapors are then fluorinated as they pass through the remaining part of the vessel. In certain instances, halocarbon reactant may be heated in a vessel separate from the fluorinatlon vessel, a stream of inert gas, such as nitrogen,

hydrogen fluoride, or helium, passed through the heated liquid, and the mixed vapors of inert gas and of saturated halocarbon reactant then passed into the fluorination vessel. Fluorination with the halocarbon reactant .in the vapor phase is conveniently carried out at atmospheric pressure although it may, if desired, be carried out at a pressure higher or lower than atmospheric pressure.

Although fluorlnation of a saturated halocarbon in the vapor phase using cerium tetrafluoride as the-active fluorinatin-g agent is usually carried out at a temperaturebetween about 50 C., and about 600 C., it may be carried out at any convenient temperature above the condensing temperature of the vapors at the reaction pressure. In certain instances, the temperature of fluorinatlon may even be maintained sufliciently high to cause fluorinoly'sis. Temperatures sufliciently high to cause the formation of substantial amounts of undesirable by-products are to be avoided. 3

After the cerium tetrafluoride has been largely exhausted and converted substantially to cerium trifluoride the reaction vessel may be purged with nitrogen or other inert, gas to free it from most of the organic substances before elemental fluoride may be mixed together in any conven= ient way, e. g., the halocarbon may be stirred in a vessel at the desired temperature and cerium tetrafluoride added gradually thereto. Such pro cedure with the halocarbon reactant in the liquid phase is of particular value when the halocarbon boils at a high temperature. It has been found that the ratio of the amount of cerium tetrafluoride to the amount of saturated halocarbon reactant necessary when a high degree of fluorination is to be effected is so great that when the reaction is carried out with the halocarbon reactant in liquid phase the final reaction mixture is frequently of a moist granular nature rather than of a fluid nature and is dimcult to handle on a large scale. This diiflculty may be overcome in a number of ways. Thus the liquid which is to be fluorinated may be diluted with a liquid inert under the reaction conditions, such as a high-boiling fluorocarbon, to increase the proportion of liquid in the reaction mixture. Alternatively, fluorinatlon in the liquid phase may be carried out step-wise. Thus in the first step the addition of solid cerium tetrafluoride to the liquid halo carbon reactant may be stopped while the mixture is still fluid enough to be agitated readily. The reaction product may be filtered or otherwise treated to separate the' organic and inorganic portions thereof. the spent cerium fluoride regenerated with fluorine, and the partially fluorinated organic portion then fluorinated further by adding to it fresh or regenerated cerium tetrafluoride. Although the invention is not limited to vapor phase procedures, it is readily apparent that in many instances the fluorinatlon reaction is more conveniently carried out in vapor phase.

The degree of fluorinatlon effected is dependent, among other factors, upon the reaction teme perature and the time of contact of the halocarbon reactant with cerium tetrafluoride. In order to effect a high degree of fluorinatlon, e.g., perfluorination of a saturated halocarbon in the vapor phase during a single pass through the reaction vessel, it may be necessary to pass the halocarbon vapor very slowly through the vessel thus limiting the rate at which a highly fluorinated product may be produced in any particular reaction vessel. It has also been found that many halocarbons are somewhat more thermally unstable in the unfiuorinated or only lowly fluorinated state than when they are more highly fluorinated and that, when it is attempted to fluorinate such unfluorinated or lowly fluorinated halocarbons to produce a highly fluorinated halocarbon during a single pass of the vapor through the fluorinatlon vessel, it may be necessary to elevate the temperature to such a degree that undesirable decomposition of the halocarbon reactant may occur before substantial fluorinatlon is effected. I

, For these and other reason, it is sometimes convenient and desirable to recycle the halocarnated. usually after the spent cerium fluoride hasheenregeneratedtoinsuretherebeingahigh g ium tetrafluoride in the cerium pro recovering the desired fluorine-containing halofluoride mass. This recycling of the organic product may be repeated as many times as is desir-.

able or ry to introduce the desired proportion of fluorine into the molecule and each recycling is preferably, but not necessarily. carried out at a temperature higher than the preceding one. In this way, the first stages of fluorination, which do not require high temperatures and during which relatively unstable halocarbons may be present in the fluorination vessel, are carried out at a relatively low temperature while later stages of fluorination, which usually require a higher temperature and during which only relatively stable fluorine-containing halocarbons are present in the fluorination vessel, are carried out at content of the insuiilciently fluorinated halocarbon increased by furthertreatment with fresh or regenerated cerium tetrafluoride. Other ways 0! carbon'from the reaction mixture will be apparent to these familiar with the extend the present inventilonis not limited as to such methods of recovery.

10 Certain advantages of the invention are ap parent from the following examples, which are included by way of illustration only and arenot to be construed as limiting.

Example 1 concentrated nitric acid. and suiilcient aqueous hydrogen fluoride added to precipitate the cerium as cerium trifluoride. The precipitated cerium a higher temperature. The same effect may be 90 fluoride W88 Bemmted 3 d n i e 1 1- obtained by passing the halocarbon reactant through a number or reaction vessels or towers in series each containing cerium tetrafluoride and each maintained at a reaction temperature which may, if desired, be higher than that of the preceding vessel. By a suitable arrangement of a number of reaction vessels in series the process may be carried out continuously, it being only necessary to by-pass the vapors of the halocarbon reactant around any one of the reaction vessels while the spent cerium tetrafluoride therein is being regenerated with fluorine.

It is to be noted that a chlorine, bromine or iodine atom replaced with a fluorine atomduring the fluorination appears in the reactionproduct in elemental form. The emuent vapors from the reaction thus contain-in addition to the desired eflluent vapors and treating the condensed liquid to separate therefrom the desiredsaturated fluorine-containing halocarbon'. The liquid reaction product may be treated in any one of a number of ways. Thus the liquid may be fractionally distilled and the desired fraction collected, or it may be treated directly with a dilute aqueous alkali to free it from elemental halogen and then fractionally distilled. In any event, the desired fluorine-containing fraction may be collected and any less highly fluorinated fraction may, if desired, be recycled to the fluorination reaction vesgel to increase the proportion of fluorine in the fraction.

In the case of fluorination with the saturated halocarbon reactant in the liquid state, the reaction mixture may be filtered or otherwise treated to separate the organic and inorganic'constimainly of spent cerium tetrafiuoride, may be natant liquid and the trifluoride washed several times with water. The washed product was dried. broken up into coarse granules and packed loosely into .a tubular nickel reactor. Elemental g5 fluorine was over the cerium trifluoride for three hours at 230 C. The temperature was then raised to 470 C. and the solid again treated with elemental fluorine for several hours. A large proportion of the cerium trifluoride'was 30 thus converted to cerium tetrafluoride and this product was utilized without. removal from the fluorination reactor in the subsequent fluorinetion of saturated halocarbons.

actor containing an excess of cerium tetrafluoride heated at about 300 C; Effluent vapors from 40 the reactor are passed through a cooled receiver to condense organic products therein. The condensed liquid is washed with water and dilute alkali and fractionally distilled. Fractions are obtained containing substantial proportions. of dichlorohexafiuoropropane, trichloropentafluoropropane, and tetrachloro tetraiiuoropropane.

The fractions of chlorofluoropropanes just described are each vaporized and recycled through a reactor packed with cerium tetrafluoride at a temperature of about 350 C. In each case products are obtained having a higher fluorine content and a lower chlorine content than the fraction fluorinated. Minor fractions of perthrough a reactor containing cerium tetrafluorlde'at a temperature of about 400 C. The effluent vapors are cooled to condense organic substances therein and the condensate washed and fractionally distilled. Fractions are obtained corresponding to monochloroundecafluorocyclohexane and perfluorocyclohexane.

Example 4 One of cerous oxalate was dissolved in Hexachlonidodecafluorodecahydronaphthalene dried, or washed with alow-boiling organic liquid is added in a reactor containing cerium tetraand dried. and then regenerated with elemental fluoride at a temperature of about 400 C. After fluorine and recycled in the process. The organic several hours the reactor is purged with nitrogen halogen and the mixture then fractionslly disconstitutentsmaybewashed with waterandwith to to remove most of the organic material, the dilute aqueous alkali to free them from elemental eiiiuent vapors from the entire process being cooled in a receiver. The organic product thus' tilled. Inert liquid diluents and insuiiiclently collected is found to consist of a chlorofluoro-1 fluorinated halocarbons collected during the disdecahydronaphthalene producthaving a higher tillation-may be returned, either together or len- 15 percentage of fluorine and a lower percentage of" i chlorine than the original product fluorinated.

Upon fractionally distilling the product, fractions are obtained having compositions corresponding to tetrachlorotetradecafluorodecahydrcnaphthalene and trichloropentadecafluorodecahydronaphthalene.

Each of these latter substances upon fluorination with cerium tetrafluoride at a temperature of about 425 C. yields a product containing a substantial proportion of perfluorodecahydronaphthalene.

We claim:

1. The process for the replacement, with fluoripe, of halogen atoms other than fluorine in a saturated halocarbon with retention of the carbon structure of the molecule, which includes the steps of (1) vaporizing a saturated halocarbon containing at least one halogen atom other than fluorine, (2) maintaining solid cerium tetrafluoride in a reaction zone at a temperature between about 100 and about 600 degrees centigrade, (3) causing the vapor of the saturated halocarbon and cerium tetrafluoride to react with replacement, with fluorine, of halogen other than fluorine in the molecule of the saturated halocarbon, and (4) condensing from the eflluent product a saturated halocarbon having the same carbon structure as the starting material wherein at least one halogen atom other than fluorine has been replaced with fluorine.

2. The process of claim 1, wherein the emuent product is recycled at a temperature between 100 and 600 degrees centigrade in contact with cerium tetrafluoride until all or the halogen other than fluorine in the starting halocarbon has been replaced with fluorine, and wherein a saturated fluorocarbon is condensed from the flnal efliuent product.

3. The process of claim 1, wherein the starting saturated halocarbon is a chlorofluoropropane.

4. The process of claim 1, wherein the starting saturated halocarbon is an alicyclic halocarbon.

5. The process of claim 1, wherein the starting saturated halocarbon is a chlorofluorocyciohexane.

i0 6. The process of claim 1, wherein the starting saturated halocarbon is a chlorofluorodecahydronaphthalene. I

' EARL T. McBEE.

RICHARD M. ROBB. WALDO B. LIGE'IT.

REFERENCES crrnn The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 2,004,932 Daudt et a1, June 18, 1935 2,013,035 Daudt et al. Sept. 3, 1935 2,024,008 Midgley et al. Dec. 10, 1935 2,062,743 Daudt et al. Dec. 1, 1936 2,192,143 Midgley et al Feb. 27, 1940 2,220,713 Grcsse et al. Nov. 5, 1940 2,238,242 Balon et al. Apr. 15, 1941 2,423,045 Passino et al. June 24, 1947 FOREIGN PATENTS Number Country Date 214,293 Great Britain Apr. 14, 1924 429,591 Great Britain May 28, 1935 3141/31 Australia Jan. 20, 1933 786,123 France June 3, 1935 OTHER REFERENCES Henne et al.: J. A. C. 8., vol. 63, pp. 3478-3479 

1. THE PROCESS FOR THE REPLACEMENT, WITH FLUORINE, OF HALOGEN ATOMS OTHER THAN FLUORINE IN A SATURATED HALOCARBON WITH RETENTION OF THE CARBON STRUCTURE OF THE MOLECULE, WHICH INCLUDES THE STEPS OF (1) VAPORIZING A SATURATED HALOCARBON CONTAINING AT LEAST ONE HALOGEN ATOM OTHER THAN FLUORINE, (2) MAINTAINING SOLID CERIUM TETRAFLUORIDE IN A REACTION ZONE AT A TEMPERATURE BETWEEN ABOUT 100 AND ABOUT 600 DEGREES CENTIGRADE, (3) CAUSING THE VAPOR OF THE SATURATED HALOCARBON AND CERIUM TETRAFLUORIDE TO REACT WITH REPLACE MENT, WITH FLUORINE, OF HALOGEN OTHER THAN FLUORINE IN THE MOLECULE OF THE SATURATED HALOCARBON AND (4) CONDENSING FROM THE EFFLUENT PRODUCT A SATURATED HALOCARBON HAVING THE SAME CARBON STRUCTURE AS THE STARTING MATERIAL WHEREIN AT LEAST ONE HALOGEN ATOM THAN FLUORINE HAS BEEN REPLACED WITH FLUORINE. 